CN104415737A - Magnesium-based metal organic framework material for methane-nitrogen adsorption separation and preparation - Google Patents
Magnesium-based metal organic framework material for methane-nitrogen adsorption separation and preparation Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/04—Purification or separation of nitrogen
- C01B21/0405—Purification or separation processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
Abstract
The invention relates to a magnesium-based metal organic framework material for methane-nitrogen adsorption separation and a preparation method. The metal organic framework material is formed by coordination of at least one metal compound with at least one organic ligand to generate a framework material; the metal ions in the metal compound comprise one or more than one of Mg (II), Ni (II), Cu (II), Zn (II), Co (II), and Ca (II), and at least one metal ion is Mg (II); the organic ligand is a monodentate or polydentate organic compound of carboxylic acid or its derivatives. The invention also relates to an application of the porous magnesium-based organic framework material in methane-nitrogen adsorption separation.
Description
Technical field
The invention belongs to the design preparation of new adsorbent, the technical field of adsorptive separation engineering of mist, be specifically related to the magnesium-base metal organic framework material for methane-nitrogen adsorption separation and preparation.
Background technology
Energy and environment problem is current and the large basic problem of sustainable development closely-related two.After entering 21 century, economy causes environmental problem to highlight to depending on unduly of the energy, the rapid growth of China's economy proposes powerful rigid demand to energy-consuming, but current energy-consuming general layout of taking as the leading factor with coal and oil, the natural environment of China's fragility be can't bear the heavy load.Methane is a kind of high-grade fuel, large at occurring in nature reserves, calorific value is high, and has the highest H/C ratio, is the energy more cleaned than coal and oil.2010, in China's energy consumption structure, natural gas only accounted for 4%.For this reason, China proposes natural gas to bring up to 8.3% of the year two thousand twenty in the ratio of primary energy.Expect the year two thousand twenty, the resource gap of China's natural gas will reach 1,500 hundred million m
3.
Coal bed gas is an important supplement source of methane, and China's coal bed gas resource total amount reaches 31.46 trillion m
3, be equivalent to land conventional gas total resources (30,000,000,000,000 m of China
3), be the third-largest coal bed gas reserves state after Russia, Canada.But due to China's complex geologic conditions and corresponding supporting technology start late, especially the efficient purification technique of coal bed gas is immature, causes the coal bed gas whole utilization level of China on the low side.
The coal bed gas of exploiting out is after the pretreatment such as desulfurization, deoxidation and drying, and composition is with CH
4and N
2be main, so the concentrate of coal bed gas is exactly CH after pretreatment
4with N
2separation.Current for CH
4/ N
2be separated, the technology of R and D mainly contains separation by deep refrigeration, membrane separation process, chemical absorbing partition method and adsorption method of separation.Wherein, pressure-variable adsorption (Pressure Swing Adsorption, PSA) technology becomes the CH of this field most application prospect at present because technique is simple, small investment, adaptability are good, product gas concentration is high
4/ N
2separation method.PSA method separation of C H
4/ N
2the key of technology be adsorbent.
The current adsorbent for methane nitrogen separation mainly contains: active carbon (AC), carbon molecular sieve (CMS), mesoporous material, zeolite molecular sieve and ETS-4.Active carbon pore structure is flourishing, specific area is higher, is current the most widely used adsorbent, except the active carbon of BPL company exploitation is to CH
4/ N
2separation factor can reach 4.5 beyond (Sep.Sci.Techn., 2000,35 (5), 667), the CH of other merchandise active carbon
4/ N
2adsorbing separation effect all can not reach the requirement of commercial Application, and in PSA application process, the easy efflorescence of active carbon, gas internal circulating load is large, inefficiency.Along with the exploitation of the adsorbent of molecular sieve of function admirable, active carbon normal and they be combined, to improve CH
4the rate of recovery.The result that Ackley etc. (AIChE J., 1990,36 (8), 1229) study carbon molecular sieve shows, the sorption potential of CMS is limited.Clinoptilolite is separation of C H in zeolite molecular sieve
4/ N
2the adsorbent of most prospect, modified through different ions, its CH
4/ N
2equilibrium separation selectivity ratios has larger change, but mutually suppresses due to the kinetic selectivity of two components on clinoptilolite and equilibrium selective, improves CH by ion modification
4/ N
2the limited space of separating property.(the Nature such as Kuznicki, 2001,412 (6848), 720) describe ETS-4 and can realize methane molecule screening by cation exchange and heat treatment, it is the adjustable molecular sieve having development potentiality most, but cost is higher, easily being blocked by materials such as C2 for when the separation of methane gas and concentrate, need frequently to activate.
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) being development in recent years the most a kind of novel porous materials, is utilize metal-ligand complex effect between organic ligand and metal ion and a kind of class zeolite (organic zeolite analog) material having much future of supermolecule microporous network structure that self assembly is formed.This material and the conventional porous materials feature such as high adsorption capacity, pore structure high-sequential, low crystalline density, specific area, aperture shape and size be adjustable as having compared with zeolite, CNT, active carbon, the most significant advantage is to regulate and control channel surfaces character etc. by modifying organic ligand, reaches the object increased specific adsorbate absorption affinity.
When adopting metal ion and the organic ligand synthetic metals organic compound in s-or p-district, due to metal ion not easily coordination, often form slaine.But by adding coordination auxiliary agent in building-up process in solvent, the complexation process of reaction can be adjusted, improve the degree of crystallinity of framework material, the size controlling framework material crystal and pattern, organic ligand dissolving in a solvent can also be increased simultaneously, improve productive rate.
According to CH
4and N
2the difference of physico-chemical property, selects suitable metal and/or organic compound, and the pore size of regulation and control MOFs material and surface nature, just can develop the cheap novel absorption material that adsorption separation performance is excellent, synthesis is simple, physico-chemical property is stable.The object of the invention is to design preparation based on the organic framework materials of magnesium, for coal bed gas concentrate and purification to improve its utilization rate.
Summary of the invention
The object of the invention is the key issue for PSA technique concentrate and purification coal bed gas, i.e. CH
4/ N
2separation, provide a kind of magnesium-base metal organic framework material of being separated for methane-nitrogen adsorption and preparation method.
The invention provides a kind of magnesium-base metal organic framework material be separated for methane-nitrogen adsorption, this metal-organic framework material is produced skeleton structure by metallic compound and organoligand coordination and is formed; Metal ion in described metallic compound is Mg (II), Ni (II), Cu (II), Zn (II), Co (II), Ca (II) one or more metal ions, and wherein at least one metal ion is Mg (II).
Described organic ligand has the monodentate of at least one carboxylic acids or derivative or multiple tooth organic compound part, and this is derived from dicarboxylic acids, tricarboxylic acids or ester class organic compound.In organic ligand, carboxylic acid functional can be present in magnesium base framework material with the form of part or all of deprotonation.
The multiple tooth organic ligand that in the present invention, metal-organic framework materials adopts is monodentate, bidentate or three tooth carboxylic acids maybe can produce in the organic compound of the derivative of carboxylic acid functional one or more.Principle guarantees that the organic ligand containing these functional groups can produce framework material with magnesium coordination.
The monodentate organic ligand that the present invention adopts is formic acid, acetic acid, ring penta carboxylic acid, benzoic acid, phenylacetic acid, methyl formate, Ethyl formate, propyl formate, 1-naphthalene-carboxylic acid methyl esters, Isonicotinic acid, paranitrobenzoic acid, cinnamic acid, acrylic acid.Preferable formic acid, acetic acid, methyl formate, Isonicotinic acid.Particularly preferably methyl formate.
For the purpose of the present invention, the bidentate organic ligand that can mention such as dicarboxylic acids maybe can produce the organic derivative of dicarboxyl, such as,
Oxalic acid, tartaric acid, fumaric acid, maleic acid, succinic acid, 1, 6-hexane dicarboxylic acid, acetylenedicarboxylic acid, 1, 3-ring pentane dicarboxylic acid, 1, 4-cyclohexyl dicarboxylic acid, cyclohexene-2, 3-dicarboxylic acids, 1, 2-phthalic acid, 1, 3-M-phthalic acid, 1, 4-terephthalic acid (TPA), 5-tert-butyl isophthalic acid, 2, 5-dihydric para-phthalic acid, biphenyl dicarboxylic acid, 2, 3-pyridinedicarboxylic acid, pyridine 2, 3-dioctyl phthalate, 2, 5-pyridinedicarboxylic acid, 1, 4-naphthalene diacid, 2, 6-naphthalene diacid, 2, 3-naphthalenedicarboxylic acid, 2, 3-pyrazinedicarboxylicacid, anthracene-2, 3-dioctyl phthalate, imidazoles-2, 4-dicarboxylic acids, acetic anhydride, phthalic anhydride, maleic anhydride, 1, 8-naphthalene dicarboxylic acids acid anhydride, diethyl malonate, dimethyl malenate, methyl acrylate, phthalic acid ester, 1, 4-cyclohexyl dicarboxylic acid dimethyl ester,
Wherein prioritizing selection tartaric acid of the present invention, fumaric acid, 5-tert-butyl isophthalic acid, 2,5-Dihydroxyterephthalic acid, NDA, methyl acrylate one or more.
The three tooth organic ligands that the present invention relates to are: 1,3,5-benzenetricarboxylic acid, 2-hydroxy propane-1,2,3-tricarboxylic acids (citric acid), 1,3,5-tri-(4-carboxyl phenyl) benzene, all benzene tricarbonic acid's triethyl, all benzene tricarbonic acid's diethylester, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-butane tricarboxylic acid, cis-aconitic acid, trans-aconitic acid.Wherein preferably three tooth organic ligands are 1,3,5-benzenetricarboxylic acid, 1,3,5-tri-(4-carboxyl phenyl) benzene.
Present invention also offers the preparation method of the described magnesium-base metal organic framework material for methane-nitrogen adsorption separation, described reaction is completed by the method for solvent heat, and the concrete steps of the method are as follows:
(1) metallic compound, organic ligand are dissolved in solvent, wherein the molar ratio range of metallic compound and organic ligand is 1:4 to 4:1, then adds a certain amount of coordination auxiliary agent, at room temperature stirs, obtain mixed liquor;
(2) mixed liquor that step (1) obtains is reacted a period of time under certain condition;
(3) by the solids separation that step (2) produces, then wash, dry, activation.
The preparation method of the magnesium-base metal organic framework material be separated for methane-nitrogen adsorption provided by the invention, described metallic compound is any one or its mixture in chloride that metal ion is corresponding, nitrate, sulfate, acetate, subcarbonate, methoxide, ethylate, hydroxide, oxide.Preferred chloride, nitrate, sulfate, acetate.More preferably sulfate.
The preparation method of the magnesium-base metal organic framework material for methane-nitrogen adsorption separation provided by the invention, described solvent is water, methyl alcohol, ethanol, isopropyl alcohol, isobutanol, amylalcohol, ethylene glycol, 1, 2-propane diols, cyclohexanol, acetone, ether, cyclohexane, 1, 4-dioxane, N, dinethylformamide (DMF), N, N-DEF (DEF), N, N-dimethylacetylamide (DMAC), 1-METHYLPYRROLIDONE (NMP), benzene, toluene, chlorobenzene, chloroform, tetrachloromethane, oxolane (THF), one in dimethylamine or mixture.Preferred solvent is water, DMF, DEF, NMP, methyl alcohol, ethanol.Particularly preferably methyl alcohol, DMF.
Solvent miscible with water in course of reaction has methyl alcohol, ethanol, isopropyl alcohol, isobutanol, amylalcohol, ethylene glycol, 1,2-PD, cyclohexanol, and maximum water content is preferably 50 volume %, more preferably 30 volume %, particularly preferably 10 volume %.
Term " solvent " comprises the mixture of neat solvent and various solvent.
The preparation method of the magnesium-base metal organic framework material for methane-nitrogen adsorption separation provided by the invention, the pressure of described reaction is the saturated vapor pressure of solvent at respective reaction temperature, pressure, preferably more than 8 bar (definitely), very particularly preferably carries out under the pressure being no more than 4 bar.Described reaction temperature is relevant with the characteristic of solvent, and reaction temperature of the present invention can at room temperature be carried out, temperature preferably 60 DEG C ~ 180 DEG C, more preferably 80 DEG C ~ 140 DEG C.Described magnesium-base metal organic framework material synthetic reaction is carried out at least 6 hours.This reaction preferred time is greater than 12 hours.The preferred reaction time is greater than 36 hours.
Not easily coordination when Mg (II) reacts with carboxylic acids or derivative organic ligand, often form slaine, in the present invention, magnesium-base metal organic framework material is prepared in a solvent, when in solvent containing be greater than 10 % by weight water time, coordination auxiliary agent to be added in solvent, for increasing organic ligand dissolving in a solvent, the complexation process of adjustment reaction, improves the degree of crystallinity of framework material, the size controlling framework material crystal and pattern.What the use of Non-aqueous Organic Solvents made coordination auxiliary agent is added to nonessential behavior.Can select inherently to have certain coordination regulating action for solvent of the present invention, but this not definitely necessary for enforcement method of the present invention.
Coordination auxiliary agent can be used, but preferentially do not use extra coordination auxiliary agent.
The preparation method of the magnesium-base metal organic framework material be separated for methane-nitrogen adsorption provided by the invention, described coordination auxiliary agent is one in ethylenediamine tetra-acetic acid (EDTA), urea, ethylenediamine, triethylene diamine, phosphorous acid, ammoniacal liquor, triethylene tetramine, piperazine, potassium citrate, natrium citricum, porphyrin ring, sodium phosphate trimer, ortho-aminobenzoic acid, oxine, ammonium fluoride, ammonium acid fluoride, hydrogen fluoride, tetrabutyl ammonium fluoride, formic acid, acetic acid or composition.The molar ratio range of described coordination auxiliary agent and metal magnesium salts is 1:20 to 10:1, preferred 1:10, more preferably 1:4.
Solvent heat (hydro-thermal) method is the most frequently used method of synthetic metals complex, and the method technique is simple, the metal complex purity of the low synthesis of production cost is high, good crystalline and can controlling.Magnesium-base metal organic framework material in the present invention adopts the synthesis of solvent heat (hydro-thermal) method.
Magnesium-base metal organic framework material in the present invention can in the geometric shape of rule or unformed state of aggregation.
There is organic coordination compound in the hole of the magnesium-base metal organic framework material in the present invention, can pass through with non-aqueous solvent process framework material, the organic ligand in solvent extraction removing duct.
Process is preferably flooded at least 6 hours, particularly preferably at least carries out 24 hours.
Operable nonaqueous solvents is above-mentioned methyl alcohol, ethanol, isopropyl alcohol, isobutanol, amylalcohol, ethylene glycol, 1,2-propane diols, cyclohexanol, acetone, ether, cyclohexane, 1,4-dioxane, N, dinethylformamide (DMF), N, N-DEF (DEF), DMA (DMAC), 1-METHYLPYRROLIDONE (NMP), benzene, toluene, chlorobenzene, chloroform, tetrachloromethane, oxolane (THF), dimethylamine or its mixture.
Particular methanol, ethanol, acetone, ether, cyclohexane and their mixture.
The preparation method of the magnesium-base metal organic framework material for methane-nitrogen adsorption separation provided by the invention, the activation condition in described step (3) is: the immersion solvent before activation is acetone or ether, and activation temperature is 150 DEG C ~ 180 DEG C.Soak time carries out at least 4 hours, preferably at least 10 hours.In order to provide active efficiency usually to activate under vacuum, but vacuum activating in the present invention not necessarily.
Magnesium-base metal organic framework material provided by the invention comprises space, particularly micropore and/or mesopore.Micropore definition diameter is the hole of 2nm or less, and mesopore is defined as the hole that diameter range is 2nm ~ 50nm, the class definition in the hole that often kind of situation provides according to IUPAC (IUPAC).
Porous magnesium Base Metal organic framework material provided by the invention, has the specific area that Langmuir method determines and is greater than 20m
2/ g, pore size distribution range is 0.4 ~ 10nm.Larger specific area often has high adsorbance, and suitable aperture can produce steric effect to gas molecule, expands the diffusion rate difference between gas with various molecule.For CH
4/ N
2adsorption separation process demand, the magnesium-base metal organic framework material in the present invention, its preferred specific area is greater than 100m
2/ g, pore-size distribution is 0.4 ~ 1.0nm.Particularly preferably specific area is greater than 300m
2/ g, pore-size distribution is 0.4 ~ 0.5nm.
Magnesium-base metal organic framework material of the present invention is applied to CH
4with N
2the adsorbing separation of gaseous mixture.
Magnesium-base metal organic framework material for methane-nitrogen adsorption separation provided by the invention is the new adsorbent solving PSA technique concentrate coal bed gas.The CH of described magnesium-base metal organic framework material
4/ N
2equilibrium adsorption separation factor is greater than 3, preferably recommends equilibrium adsorption separation factor between 5 ~ 8.Be further characterized in that described magnesium-base metal organic framework material specific area is low but to CH
4have larger adsorbance, under 298K, 1bar, dynamic adsorbance is at least 0.3mmol/g, preferably at least 0.5mmol/g, particularly preferably at least 0.8mmol/g.
Detailed description of the invention
The following examples will be further described the present invention, but not thereby limiting the invention.
Term " separation factor " is the important parameter of option and evaluation adsorbent, may be defined as mixed gas sorption system separation factor:
Wherein, x
i, x
jbe respectively the amount of substance mark of component i, j in Adsorption Phase x; y
i, y
jbe respectively the amount of substance mark of component i in gas phase y, j; n
i, n
jbe respectively the adsorbance of component i on adsorbent, j.
By measuring the breakthrough curve of component i and j, the adsorbance of each component can be tried to achieve according to conservation of matter, thus be balanced the adsorbing separation factor.
The adsorbance wherein recorded is dynamic adsorbance.
Embodiment 1:
(1) 36.9g MgSO is taken
47H
2o and 15ml (99% formic acid) is dissolved in 850mlDMF, while constantly stirring, slowly add 2.8g ammonium fluoride, stirs 20min until evenly, obtain mixed solution; Transferred to by mixed solution with sealing in teflon-lined 1L autoclave tight, be placed in 120 DEG C of baking ovens and react 12 hours, Temperature fall is to room temperature.Centrifugal (10000rpm, 5min) sediment separate out, washes three times with ethanol, each 80ml, and then under 100 DEG C of conditions, drying obtains white powder in 6 hours.
(2) by white powder 100ml acetone soak 12 hours, filter, 170 DEG C, activate 12 hours under the vacuum of 100 millibars, form adsorbent A, weigh 14.3g.
Contrast experiment, the method according to BASF patent US2011178335A1 prepares adsorbent B respectively.
The specific area that the Langmuir method of gained adsorbent A is determined is 420m
2/ g, average pore size is 0.5nm;
Gained adsorbent A between 298K, 0-1MPa (absolute atmosphere), α CH
4/ N
2=4.5-7.0;
The CH of gained adsorbent A
4dynamic adsorbance is 0.82mmol/g (298k, 1bar);
The specific area that the Langmuir method of gained adsorbent B is determined is 345m
2/ g, average pore size is 0.49nm;
Gained adsorbent B between 298K, 0-1MPa (absolute atmosphere), α CH
4/ N
2=3.4-5.0;
The CH of gained adsorbent B
4dynamic adsorbance is 0.45mmol/g (298k, 1bar).
Embodiment 2:
(1) 49.3g MgSO is taken
47H
2o is dissolved in 720mlDMF, forms solution A; 11.2g triethylene diamine is dissolved in 50ml deionized water, forms solution B; While constantly stirring, in solution A, slowly add solution B, form Homogeneous phase mixing liquid.By 82ml (98% methyl formate) to be at the uniform velocity added dropwise to mixed liquor, stir 20min until evenly, obtain mixed solution C; Transferred to by mixed solution with sealing in teflon-lined 1L autoclave tight, be placed in 100 DEG C of baking ovens and react 24 hours, Temperature fall is to room temperature.Centrifugal (10000rpm, 5min) sediment separate out, with methanol wash column three times, each 80ml, then dryly under 100 DEG C of conditions obtains white powder in 6 hours.
(2) by white powder 100ml acetone soak 12 hours, filter, 160 DEG C, activate 12 hours under the vacuum of 100 millibars, form adsorbent C, weigh 16.1g.
The specific area that the Langmuir method of gained adsorbent C is determined is 352m
2/ g, average pore size is 0.49nm;
Gained adsorbent C between 298K, 0-1MPa (absolute atmosphere), α CH
4/ N
2=3.0-5.4;
The CH of gained adsorbent C
4dynamic adsorbance is 0.6mmol/g (298k, 1bar).
Embodiment 3:
(1) 36.9g MgSO is taken
47H
2o, 22.5g D-tartaric acid is dissolved in 607.6ml methyl alcohol (98%), while constantly stirring, slowly add 2.8g ammonium fluoride, stirs 30min until evenly, obtain mixed solution; Transferred to by mixed solution with sealing in teflon-lined 1L autoclave tight, be placed in 120 DEG C of baking ovens and react 36 hours, Temperature fall is to room temperature.Leach sediment, wash three times by deionized water, each 300ml, then by filter cake under 60 DEG C of conditions dry 10 hours, obtain milky block.
(2) by product at 130 DEG C, activate 6 hours under the vacuum of 100 millibars, form adsorbent D, weigh 23.6g.
The specific area that the Langmuir method of gained adsorbent D is determined is 208m
2/ g, average pore size is 2.4nm;
Gained adsorbent D between 298K, 0-1MPa (absolute atmosphere), α CH
4/ N
2=2.6-4.4;
The CH of gained adsorbent D
4dynamic adsorbance is 0.52mmol/g (298k, 1bar).
Embodiment 4:
(1) 24.6g Mg (AC) is taken
24H
2o dissolves in 530mlDMF, forms solution A; The 200ml cyclohexanol solution being dissolved with 9.0g fumaric acid is slowly added in solution A while constantly stirring, stirs 30min until evenly, the mixed liquid B obtained; Transferred to by mixed liquor with sealing in teflon-lined 1L autoclave tight, be placed in 100 DEG C of baking ovens and react 36 hours, Temperature fall is to room temperature.Centrifugal (10000rpm, 5min) sediment separate out, with methanol wash column three times, each 80ml, then dryly under 100 DEG C of conditions obtains white powder in 10 hours.
(2) by white powder 100ml acetone soak 12 hours, filter, 180 DEG C, activate 12 hours under the vacuum of 100 millibars, form adsorbent F, weigh 6.1g.
The specific area that the Langmuir method of gained adsorbent F is determined is 120m
2/ g, average pore size is 3.0nm;
Gained adsorbent F between 298K, 0-1MPa (absolute atmosphere), α CH
4/ N
2=2.6-4.2;
The CH of gained adsorbent F
4dynamic adsorbance is 0.38mmol/g (298k, 1bar).
Embodiment 5:
(1) 36.9g MgSO is taken
47H
2o and 21.4g2,6 naphthalenedicarboxylic acids are dissolved in 840ml volume ratio DMF/CH
3oH/H
2o is in the mixed liquor of 20:5:1, while constantly stirring, slowly add 9.8g tetrabutyl ammonium fluoride, stirs 30min until evenly, obtain suspension; Transferred to by suspension with sealing in teflon-lined 1L autoclave tight, be placed in 120 DEG C of baking ovens and react 24 hours, Temperature fall is to room temperature.Leach sediment, with methanol wash column three times, each 200ml, then by filter cake under 100 DEG C of conditions dry 6 hours, obtains product.
(2) by product 120ml acetone soak 12 hours, filter, 180 DEG C, activate 12 hours under the vacuum of 100 millibars, finally 300 DEG C of calcinings 20 hours, form adsorbent G, weigh 18.4g.
Contrast experiment, the method according to BASF patent CN101248034A prepares adsorbent H respectively.
The specific area that the Langmuir method of gained adsorbent G is determined is 510m
2/ g, average pore size is 0.9nm;
Gained adsorbent G between 298K, 0-1MPa (absolute atmosphere), α CH
4/ N
2=3.0-6.0;
The CH of gained adsorbent G
4dynamic adsorbance is 0.72mmol/g (298k, 1bar);
The specific area that the Langmuir method of gained adsorbent H is determined is 325m
2/ g, average pore size is 1.2nm;
Gained adsorbent H between 298K, 0-1MPa (absolute atmosphere), α CH
4/ N
2=3.0-5.0;
The CH of gained adsorbent H
4dynamic adsorbance is 0.43mmol/g (298k, 1bar).
Embodiment 6:
(1) 24.6g Mg (AC) is taken
24H
2o dissolves in 530mlDMF, forms solution A; To be dissolved with 16.6g1, the 200ml cyclohexanol solution of 4-terephthalic acid (TPA) and 5ml (99% formic acid) slowly adds in solution A while constantly stirring, and forms mixed liquid B; Then drip 10ml hydrofluoric acid, stir 30min until evenly, the mixed liquor C obtained; Transferred to by mixed liquor C with sealing in teflon-lined 1L autoclave tight, be placed in 140 DEG C of baking ovens and react 24 hours, Temperature fall is to room temperature.Centrifugal (10000rpm, 5min) sediment separate out, with methanol wash column three times, each 80ml, then dryly under 100 DEG C of conditions obtains white powder in 10 hours.
(2) by white powder 100ml acetone soak 12 hours, filter, 170 DEG C, activate 12 hours under the vacuum of 100 millibars, form adsorbent I, weigh 9.3g.
The specific area that the Langmuir method of gained adsorbent I is determined is 87m
2/ g, average pore size is 2.4nm;
Gained adsorbent I between 298K, 0-1MPa (absolute atmosphere), α CH
4/ N
2=2.3-4.0;
The CH of gained adsorbent I
4dynamic adsorbance is 0.31mmol/g (298k, 1bar).
Claims (11)
1., for the magnesium-base metal organic framework material that methane-nitrogen adsorption is separated, it is characterized in that: this metal-organic framework material is produced skeleton structure by metallic compound and organoligand coordination and formed;
Metal ion in described metallic compound is Mg (II), Ni (II), Cu (II), Zn (II), Co (II), Ca (II) one or more metal ions, and wherein at least one metal ion is Mg (II);
Described organic ligand is the monodentate of carboxylic acids or derivatives thereof or multiple tooth organic compound.
2. according to described in claim 1 for magnesium-base metal organic framework material that methane-nitrogen adsorption is separated, it is characterized in that: described organic ligand is formic acid, acetic acid, methyl formate, tartaric acid, fumaric acid, 5-tert-butyl isophthalic acid, 1,3-M-phthalic acid, 2,5-dihydric para-phthalic acid, 2,6-naphthalenedicarboxylic acid, 1, one or more in 3,5-tri-(4-carboxyl phenyl) benzene.
3. a preparation method for the magnesium-base metal organic framework material be separated for methane-nitrogen adsorption described in claim 1, is characterized in that: the concrete steps of the method are as follows:
(1) metallic compound, organic ligand are dissolved in solvent, add a certain amount of coordination auxiliary agent simultaneously, at room temperature stir, obtain mixed liquor;
(2) mixed liquor that step (1) obtains is reacted under certain condition;
(3) by the solids separation that step (2) produces, then wash, dry, activation.
4. according to the preparation method of the magnesium-base metal organic framework material be separated for methane-nitrogen adsorption described in claim 3, it is characterized in that: the metallic compound in described step (1) is any one or its mixture in chloride that metal ion is corresponding, nitrate, sulfate, acetate, subcarbonate, methoxide, ethylate.
5. according to the preparation method of the magnesium-base metal organic framework material be separated for methane-nitrogen adsorption described in claim 3, it is characterized in that: the solvent in described step (1) is one in water, DMF, DEF, NMP, methyl alcohol, ethanol or mixture.
6. according to the preparation method of the magnesium-base metal organic framework material be separated for methane-nitrogen adsorption described in claim 3, it is characterized in that: the coordination auxiliary agent in described step (1) is one in ethylenediamine tetra-acetic acid (EDTA), ethylenediamine, triethylene diamine, triethylene tetramine, piperazine, ammonium fluoride, sodium fluoride, ammonium acid fluoride, hydrogen fluoride, tetrabutyl ammonium fluoride, formic acid, acetic acid or composition.
7. according to the preparation method of the magnesium-base metal organic framework material be separated for methane-nitrogen adsorption described in claim 6, it is characterized in that: described coordination auxiliary agent is one in ethylenediamine, triethylene diamine, piperazine, ammonium fluoride, hydrogen fluoride, formic acid or composition.
8., according to the preparation method of the magnesium-base metal organic framework material be separated for methane-nitrogen adsorption described in claim 3, it is characterized in that: the molar ratio range of described coordination auxiliary agent metallizing thing is 1:20 to 10:1.
9. according to the preparation method of the magnesium-base metal organic framework material be separated for methane-nitrogen adsorption described in claim 3, it is characterized in that: the reaction condition in described step (2) is: reaction temperature is 60 DEG C ~ 180 DEG C, and the reaction time is at least 6 hours.
10. according to the preparation method of the magnesium-base metal organic framework material be separated for methane-nitrogen adsorption described in claim 3, it is characterized in that: the activation condition in described step (3) is: the immersion solvent before activation is acetone or ether, activation temperature is 150 DEG C ~ 180 DEG C.
For the application of the magnesium-base metal organic framework material of methane-nitrogen adsorption separation described in 11. claims 1, it is characterized in that: this magnesium-base metal organic framework material is applied to CH
4with N
2the adsorbing separation of gaseous mixture.
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101454260A (en) * | 2006-03-29 | 2009-06-10 | 巴斯夫欧洲公司 | Method for commercially obtaining propene |
CN101585856A (en) * | 2008-05-23 | 2009-11-25 | 安徽大学 | With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation |
WO2010148276A2 (en) * | 2009-06-19 | 2010-12-23 | The Regents Of The University Of California | Carbon dioxide capture and storage using open frameworks |
CN101977881A (en) * | 2008-03-17 | 2011-02-16 | 巴斯夫欧洲公司 | Use of formiate-based porous organometallic framework materials for storing methane |
US8227375B2 (en) * | 2008-09-12 | 2012-07-24 | Uop Llc | Gas adsorption on metal-organic frameworks |
CN102962037A (en) * | 2012-11-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
CN102962036A (en) * | 2012-10-30 | 2013-03-13 | 中国科学院大连化学物理研究所 | Porous metal organic framework material based on transition metal cobalt and preparation method thereof |
-
2013
- 2013-08-23 CN CN201310375618.1A patent/CN104415737A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101454260A (en) * | 2006-03-29 | 2009-06-10 | 巴斯夫欧洲公司 | Method for commercially obtaining propene |
CN101977881A (en) * | 2008-03-17 | 2011-02-16 | 巴斯夫欧洲公司 | Use of formiate-based porous organometallic framework materials for storing methane |
CN101585856A (en) * | 2008-05-23 | 2009-11-25 | 安徽大学 | With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation |
US8227375B2 (en) * | 2008-09-12 | 2012-07-24 | Uop Llc | Gas adsorption on metal-organic frameworks |
WO2010148276A2 (en) * | 2009-06-19 | 2010-12-23 | The Regents Of The University Of California | Carbon dioxide capture and storage using open frameworks |
WO2010148276A3 (en) * | 2009-06-19 | 2011-04-21 | The Regents Of The University Of California | Carbon dioxide capture and storage using open frameworks |
CN102962036A (en) * | 2012-10-30 | 2013-03-13 | 中国科学院大连化学物理研究所 | Porous metal organic framework material based on transition metal cobalt and preparation method thereof |
CN102962037A (en) * | 2012-11-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
XIAOFEI WU等: "Microwave synthesis and characterization of MOF-74 (M = Ni, Mg) for gas separation", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
ZONGBI BAO等: "Adsorption of CO2 and CH4 on a magnesium-based metal organic framework", 《JOURNAL OF COLLID AND INTERFACE SCIENCE》 * |
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